CN103647001A - Flocked transparent conductive film and preparation method thereof - Google Patents
Flocked transparent conductive film and preparation method thereof Download PDFInfo
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- CN103647001A CN103647001A CN201310532651.0A CN201310532651A CN103647001A CN 103647001 A CN103647001 A CN 103647001A CN 201310532651 A CN201310532651 A CN 201310532651A CN 103647001 A CN103647001 A CN 103647001A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 87
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000002253 acid Substances 0.000 claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 29
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 27
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims description 140
- 239000011248 coating agent Substances 0.000 claims description 139
- 235000008216 herbs Nutrition 0.000 claims description 41
- 210000002268 wool Anatomy 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 19
- 239000010408 film Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- 238000005530 etching Methods 0.000 description 9
- 238000005240 physical vapour deposition Methods 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000011260 aqueous acid Substances 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- 229960001296 zinc oxide Drugs 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02697—Forming conducting materials on a substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to the technical field of solar cells, and discloses a flocked transparent conductive film and a preparation method thereof. The preparation method of the flocked transparent conductive film comprises the following steps: the temperature of a substrate on which a transparent conductive film is formed is adjusted to a temperature range from 18 DEG C to 25 DEG C; flocking is performed on the temperature-adjusted transparent conductive film in acid liquor, wherein the flocking time is in the range from 30 seconds to 100 seconds, and the acid liquor contains, on a weight basis, 0.0365%-0.365% hydrogen chloride, 0.04%-0.4% hydrogen fluoride, 0.1%-0.5% oxalic acid and 0.1%-0.5% acetic acid; and then the flocked transparent conductive film is cleaned. The flocked transparent conductive film obtained by the flocked transparent conductive film preparation method of the invention has the advantage of good flocking uniformity and can be applied in the production of large-area transparent conductive films.
Description
Technical field
The present invention relates to technical field of solar batteries, particularly relate to a kind of matte nesa coating and preparation method thereof.
Background technology
In recent years, as the photovoltaic cell of regenerative resource and the development of large area photovoltaic module, caused people's extensive concern.Especially amorphous silicon and nano microcrystalline silicon laminated cell, emerge rapidly with its unique advantage, becomes the main product of market application.Transparent conductive oxide film is absolutely necessary as the transparency electrode of silicon-based thin film solar cell, and Al-Doped ZnO (Al-doped ZnO, be called for short AZO) abundant raw materials of nesa coating, nontoxic, low price, and in hydrogen plasma good stability; And because the AZO nesa coating (being matte AZO nesa coating) of light trapping structure has larger surface roughness, can realize incident sun reflection of light, refraction and scattering, the light inciding in film is distributed to all angles, thereby increase the light path of incident light in battery through multiple reflections, increase the absorption of light to increase the short circuit current of battery, improve the electricity conversion of battery.Therefore, the solar energy photovoltaic glass that the AZO thin-film material of take is master is considered to next Developing mainstream, and batch production large area matte AZO transparent conducting film glass is with historically new significance to the development of photovoltaic industry.
The producer of now studying in the world new A ZO film is many, but is only the laboratory research stage that rests on mostly, also there is no the report of large scale and scale matte AZO nesa coating successful Application at present.The research emphasis of prior art is the adjustment to physical vapour deposition (PVD) (Physical Vapor Deposition is called for short PVD) magnetron sputtering technique parameter.The preparation method of existing a kind of pile face zinc oxide (ZnO) transparent conductive film, by magnetron sputtering technique parameter is regulated and obtains ZnO nesa coating, adopt again dilute hydrochloric acid solution to carry out wet chemical etch to it and prepare Textured ZnO Transparent Conductive Thin Film, owing to adopting watery hydrochloric acid to carry out making herbs into wool, etch rate is very fast, controllability is poor, therefore, the matte uniformity of the matte nesa coating obtaining is poor, and this scheme only can be applicable among the preparation of laboratory small size matte nesa coating.
Summary of the invention
The object of this invention is to provide a kind of matte nesa coating and preparation method thereof, in order to improve the matte uniformity of matte nesa coating, and then matte nesa coating is applied among the production of large area matte nesa coating.
The preparation method of matte nesa coating of the present invention, comprising:
The substrate temperature that is formed with nesa coating is adjusted to 18 ℃～25 ℃;
In acid solution, the nesa coating of adjusting after temperature is carried out to making herbs into wool, making herbs into wool duration is 30～100 seconds, wherein, described acid solution by weight percentage, contain 0.0365%～0.365% hydrogen chloride, 0.04%～0.4% hydrogen fluoride, 0.1%～0.5% oxalic acid and 0.1%～0.5% acetic acid;
Nesa coating after making herbs into wool is cleaned.
In technical solution of the present invention, process for etching is studied, find first to adjust the temperature to 18 ℃ of nesa coating～25 ℃, then adopt and contain hydrogen chloride (HCl), hydrogen fluoride (HF), oxalic acid (HOOC-COOH) and acetic acid (CH
3cOOH) acid solution is carried out the pattern of matte nesa coating of making herbs into wool formation to nesa coating better, and can improve the uniformity of matte, described acid solution is for containing hydrogen chloride, hydrogen fluoride, oxalic acid and vinegar aqueous acid, if the weight fraction of HCl and HF is larger, etching pit is excessive, corrosion rate is very fast, and is difficult to control uniformity; If the weight fraction of HCl and HF is less, etching depth is inadequate, and the concave-convex effect of suede structure is not obvious; If the weight fraction of oxalic acid and acetic acid is larger, the extremely difficult control of etching speed, causes suede structure poor repeatability; If the weight fraction of oxalic acid and acetic acid is less, corrosion rate is slower, is unfavorable for the ageing and stability of batch production.The preparation method of matte nesa coating is applied in solar cell, can improves the short circuit current of battery, and then improve electricity conversion.
Preferably, described acid solution contains 0.0365%～0.182% hydrogen chloride, 0.04%～0.2% hydrogen fluoride, 0.1%～0.3% oxalic acid and 0.1%～0.3% acetic acid.Adopt the acid solution in technical scheme preferably to carry out making herbs into wool to nesa coating, the matte uniformity of the matte nesa coating obtaining is better.
Preferably, described acid solution contains 0.182% hydrogen chloride, 0.08% hydrogen fluoride, and 0.2% oxalic acid and 0.1% acetic acid, or described acid solution contains 0.0365% hydrogen chloride, 0.04% hydrogen fluoride, 0.1% oxalic acid and 0.1% acetic acid; Or described acid solution contains 0.182% hydrogen chloride, 0.2% hydrogen fluoride, 0.3% oxalic acid and 0.3% acetic acid.
Preferably, described making herbs into wool duration is 30 seconds, 50 seconds, 60 seconds, 100 seconds or 120 seconds.
Particularly for described acid solution, contain 0.182% hydrogen chloride, 0.08% hydrogen fluoride, 0.2% oxalic acid and 0.1% acetic acid, when making herbs into wool duration is 60 seconds, adopt the acid solution in this technical scheme to carry out making herbs into wool to nesa coating, the matte crest scope 50～150nm of the matte nesa coating obtaining, trough scope is 50～150nm, and width is 100～300nm, and roughness is 25～40nm, the width of the visible matte obtaining is consistent with the degree of depth, and uniformity is better.
Preferably, describedly the substrate temperature that is formed with nesa coating is adjusted to 18 ℃～25 ℃ is specially: the substrate that is formed with nesa coating is infiltrated in the deionized water of 18 ℃～25 ℃, make its temperature be adjusted to 18 ℃～25 ℃.
Preferably, describedly the substrate temperature that is formed with nesa coating is adjusted to 18 ℃～25 ℃ is specially: the substrate temperature that is formed with nesa coating is adjusted to 18 ℃, 20 ℃ or 25 ℃.
In this technical scheme, the nesa coating that first need to carry out making herbs into wool carries out temperature adjustment, is beneficial to making herbs into wool, and suitable temperature range is 18 ℃～25 ℃, preferred scope is 18 ℃～20 ℃, and for example temperature is 18 ℃, 19 ℃, 20 ℃, 22 ℃, 24 ℃ or 25 ℃.Adopt deionized water to infiltrate, when nesa coating is adjusted to suitable temperature, also nesa coating has been carried out to prerinse.Certainly, also can adopt additive method to adjust carrying out the temperature of the nesa coating of making herbs into wool, such as air knife etc.
Preferably, described nesa coating adopts the method for magnetron sputtering plating on substrate, to form nesa coating.For example, adopt the technological parameter of thing PVD magnetron sputtering to be: gas pressure intensity is 0.1～1.0Pa ar gas environment, and underlayer temperature is 0～300 ℃, and direct current sputtering power is 1～60kW.
Preferably, described nesa coating after making herbs into wool is cleaned and is specially: the nesa coating after adopting deionized water to making herbs into wool cleans.Nesa coating is in acid solution after making herbs into wool, its surface is more residual acid solutions also, therefore need to the nesa coating after making herbs into wool be cleaned, the nesa coating after generally adopting deionized water to making herbs into wool cleans, and after being dried, obtains clean matte nesa coating.
Preferably, the material of described nesa coating is Al-Doped ZnO, and wherein the doping content of aluminium is 1%～1.2%, and for example the doping content of aluminium is 1%, 1.1%, 1.15% or 1.2%.
Preferably, the thickness of described nesa coating is 700～1200nm(nanometer), for example, thickness is 700nm, 900nm, 1000nm, 1100nm or 1200nm, more excellent, the thickness of described nesa coating is 1000nm.
Matte nesa coating of the present invention, the preparation method by above-mentioned any matte nesa coating obtains.The matte nesa coating obtaining by above-mentioned any preparation method, has good matte uniformity, can be used for obtaining large area matte nesa coating.
The matte nesa coating that the present invention obtains can be deposited in glass substrate, can deposition of amorphous silicon films on matte nesa coating, then on amorphous silicon membrane depositing metal layers, form silicon-based film solar cells.
The application of the preparation method who the invention still further relates to above-mentioned matte nesa coating in solar cell is made.
In the preparation method of matte nesa coating provided by the present invention, hydrogen chloride can electrolysis goes out hydrogen ion and reacts with the oxide in nesa coating, forms metal ion, for example, can react with the zinc oxide in zinc-oxide film, forms zinc ion.Meanwhile, the relative hydrone of acetic acid molecule is larger, and it is sterically hindered larger, can stop that hydrogen ion moves to zinc oxide surface, and then can slow down reaction rate, improve surface uniformity, and then can be applied among the making of matte nesa coating of area battery.And, the preparation method of matte nesa coating is applied in solar cell, can improve the short circuit current of battery, and then improve electricity conversion.
Embodiment
In order to improve the matte uniformity of matte nesa coating, the embodiment of the present invention provides a kind of matte nesa coating and preparation method thereof.In this technical scheme, first adjust the temperature to 18 ℃ of nesa coating～25 ℃, adopt again and contain hydrogen chloride, hydrogen fluoride, oxalic acid and vinegar aqueous acid nesa coating is carried out to making herbs into wool, the pattern of the matte nesa coating forming is better, and can improve the uniformity of matte, and the preparation method of matte nesa coating is applied in solar cell, can improve the short circuit current of battery, and then improve electricity conversion.For making the object, technical solutions and advantages of the present invention clearer, by the following examples the present invention is described in further detail.
The embodiment of the present invention provides a kind of preparation method of matte nesa coating, comprising:
The substrate temperature that is formed with nesa coating is adjusted to 18 ℃～25 ℃;
In acid solution, the nesa coating of adjusting after temperature is carried out to making herbs into wool, making herbs into wool duration is 30～100 seconds, wherein, described acid solution by weight percentage, contain 0.0365%～0.365% hydrogen chloride, 0.04%～0.4% hydrogen fluoride, 0.1%～0.5% oxalic acid and 0.1%～0.5% acetic acid;
Nesa coating after making herbs into wool is cleaned.
In the technical scheme of the embodiment of the present invention, process for etching is studied, find first to adjust the temperature to 18 ℃ of nesa coating～25 ℃, then adopt and contain hydrogen chloride (HCl), hydrogen fluoride (HF), oxalic acid (HOOC-COOH) and acetic acid (CH
3cOOH) acid solution is carried out the pattern of matte nesa coating of making herbs into wool formation to nesa coating better, and can improve the uniformity of matte, described acid solution is for containing hydrogen chloride, hydrogen fluoride, oxalic acid and vinegar aqueous acid, if the weight fraction of HCl and HF is larger, etching pit is excessive, corrosion rate is very fast, and is difficult to control uniformity; If the weight fraction of HCl and HF is less, etching depth is inadequate, and the concave-convex effect of suede structure is not obvious; If the weight fraction of oxalic acid and acetic acid is larger, the extremely difficult control of etching speed, causes suede structure poor repeatability; If the weight fraction of oxalic acid and acetic acid is less, corrosion rate is slower, is unfavorable for the ageing and stability of batch production.The preparation method of matte nesa coating is applied in solar cell, can improves the short circuit current of battery, and then improve electricity conversion.
The present invention's one preferred embodiment, described acid solution contains 0.0365%～0.182% hydrogen chloride, 0.04%～0.2% hydrogen fluoride, 0.1%～0.3% oxalic acid and 0.1%～0.3% acetic acid.Adopt the acid solution in technical scheme preferably to carry out making herbs into wool to nesa coating, the matte uniformity of the matte nesa coating obtaining is better.
The present invention's one preferred embodiment, described acid solution contains 0.182% hydrogen chloride, 0.08% hydrogen fluoride, 0.2% oxalic acid and 0.1% acetic acid, or described acid solution contains 0.0365% hydrogen chloride, 0.04% hydrogen fluoride, 0.1% oxalic acid and 0.1% acetic acid; Or described acid solution contains 0.182% hydrogen chloride, 0.2% hydrogen fluoride, 0.3% oxalic acid and 0.3% acetic acid.
Preferably, described making herbs into wool duration is 30 seconds, 50 seconds, 60 seconds, 100 seconds or 120 seconds.
Preferably, described acid solution contains 0.182% hydrogen chloride, 0.08% hydrogen fluoride, and 0.2% oxalic acid and 0.1% acetic acid, described making herbs into wool duration is 60 seconds.Adopt this preferably the acid solution in technical scheme nesa coating is carried out to making herbs into wool, the matte crest scope 50～150nm of the matte nesa coating obtaining, trough scope is 50～150nm, width is 100～300nm, roughness is 25～40nm, the width of the visible matte obtaining is consistent with the degree of depth, and uniformity is better.
Preferably, describedly the substrate temperature that is formed with nesa coating is adjusted to 18 ℃～25 ℃ is specially: the substrate temperature that is formed with nesa coating is adjusted to 18 ℃, 20 ℃ or 25 ℃.
Another preferred embodiment of the present invention, describedly the substrate temperature that is formed with nesa coating is adjusted to 18 ℃～25 ℃ is specially: the substrate that is formed with nesa coating is infiltrated in the deionized water of 18 ℃～25 ℃, make its temperature be adjusted to 18 ℃～25 ℃.
In this embodiment, the nesa coating that first need to carry out making herbs into wool carries out temperature adjustment, is beneficial to making herbs into wool, and suitable temperature range is 18 ℃～25 ℃, preferred scope is 18 ℃～20 ℃, and for example temperature is 18 ℃, 19 ℃, 20 ℃, 22 ℃, 24 ℃ or 25 ℃.Adopt deionized water to infiltrate, when nesa coating is adjusted to suitable temperature, also nesa coating has been carried out to prerinse.Certainly, also can adopt additive method to adjust carrying out the temperature of the nesa coating of making herbs into wool, such as air knife etc.
Another preferred embodiment of the present invention, described nesa coating adopts the method for magnetron sputtering plating on substrate, to form nesa coating.For example, adopt the technological parameter of thing PVD magnetron sputtering to be: gas pressure intensity is 0.1～1.0Pa ar gas environment, and underlayer temperature is 0～300 ℃, and direct current sputtering power is 1～60kW.
Preferably, described nesa coating after making herbs into wool is cleaned and is specially: the nesa coating after adopting deionized water to making herbs into wool cleans.Nesa coating is in acid solution after making herbs into wool, its surface is more residual acid solutions also, therefore need to the nesa coating after making herbs into wool be cleaned, the nesa coating after generally adopting deionized water to making herbs into wool cleans, and after being dried, obtains clean matte nesa coating.
For above-mentioned arbitrary embodiment, the material of described nesa coating is Al-Doped ZnO, and wherein the doping content of aluminium is 1%～1.2%, and for example the doping content of aluminium is 1%, 1.1%, 1.15% or 1.2%.
In addition, the thickness of described nesa coating is 700～1200nm(nanometer), for example, thickness is 700nm, 900nm, 1000nm, 1100nm or 1200nm, more excellent, the thickness of described nesa coating is 1000nm.
The embodiment of the present invention also provides a kind of matte nesa coating, and the preparation method of the matte nesa coating by above-mentioned arbitrary embodiment obtains.The matte nesa coating obtaining by above-mentioned any preparation method, has good matte uniformity, can be used for obtaining large area matte nesa coating.
The matte nesa coating that the present invention obtains can be deposited in glass substrate, can depositing silicon base film on matte nesa coating, then on silica-base film depositing metal layers, form silicon-based film solar cells.
Below enumerate embodiment and illustrate matte nesa coating of the present invention and preparation method thereof, in order to illustrate that matte nesa coating of the present invention and preparation method thereof can be applied to large-sized solar cell, in following examples be of a size of 2200mm*2600mm large-sized solar cell be made as example, certainly, for the solar cell of suitable size or smaller szie, technical scheme of the present invention is also applicable.And only, with the example that is made as of matte AZO nesa coating, the present invention is not limited to following embodiment.
Embodiment 1
On substrate, form AZO nesa coating, specifically comprise: substrate can adopt the ultra-clear glasses that is of a size of 2200mm*2600mm*3.2mm, ultra-clear glasses substrate is cleaned and dried, a suitable value in heated substrate to 0～300 ℃ in PVD equipment, as 180 ℃, in the ar gas environment that is 0.1～1.0Pa at gas pressure intensity, regulating direct current sputtering power is a suitable value in 1～60kW, as 30kW, carry out magnetron sputtering and prepare the AZO nesa coating that a layer thickness is 1000nm, in AZO nesa coating, the doping content of aluminium is 1wt%(weight fraction); The glass with AZO nesa coating is AZO electro-conductive glass, and the PVD equipment of employing is the magnetron sputtering apparatus of U.S. Apply Film company ATON2600 type processed;
Form matte AZO nesa coating, specifically comprise the following steps:
The AZO electro-conductive glass that device fabrication goes out to PVD adopts deionized water to infiltrate, and makes it infiltrate rear temperature and reaches 20 ℃;
In etching apparatus, carry out complex acid, the solute of acid solution is that weight fraction is 0.0365% HCl, the acetic acid that the oxalic acid that the HF that weight fraction is 0.04%, weight fraction are 0.1% and weight fraction are 0.1%, and solvent is deionized water; Those skilled in the art can form by the solution preparation by different initial concentrations according to the weight fraction of solute in above-mentioned acid solution, for example getting content is 36.5% hydrochloric acid 0.1 weight portion, hydrofluoric acid 0.1 weight portion that content is 40%, content is 99.5% oxalic acid 0.1 weight portion, and content acetic acid 0.1 weight portion that is 99% and deionized water 99.6 weight portions mix and obtain above-mentioned acid solution;
In acid solution, the AZO nesa coating of adjusting after temperature is carried out to making herbs into wool, making herbs into wool duration is 60 seconds (s);
AZO electro-conductive glass after making herbs into wool is cleaned with deionized water, with compressed air, dry, obtain matte AZO nesa coating.
Embodiment 2～7 and comparative example 1～3
The preparation process of embodiment 2～7 and comparative example 1～3 is identical with embodiment 1, and in each step, design parameter difference, the concrete technology parameter of each embodiment and each each step of comparative example is listed in table 1.
The concrete technology parameter list of each step of table 1 embodiment 1～7 and comparative example 1～3
Adopt atomic force microscope (Atomic Force Microscope, being called for short AFM) matte nesa coating that embodiment 1～7 and comparative example 1～3 are obtained tests, test result is as shown in table 2, and according to common process, prepare the solar cell with above-mentioned matte nesa coating, adopt Newport company
Short circuit current and the electricity conversion of 92193A type solar simulator test solar cell processed, test result is as shown in table 2.
The matte nesa coating of table 2 embodiment 1～7 and comparative example 1～3 and the table with test results of solar cell
By above experiment, can be found out, the matte width of embodiment 1～7 matte nesa coating that the preparation method of the matte nesa coating that the employing embodiment of the present invention provides obtains is consistent with the degree of depth, and roughness is larger, the matte nesa coating that particularly embodiment 5 makes has good matte pattern, and matte uniformity is better; And the pattern of the matte nesa coating that employing comparative example 1～3 obtains is poor, crest and trough gap are larger, and width differs.
In addition, adopt the preparation method of the embodiment of the present invention 1～7 matte nesa coating to carry out small lot (500) production AZO transparent conducting glass, the uniformity and the repeatability that obtain product are better, can reach more than 90%.And the product repeatability that the method that adopts comparative example 1～3 obtains is poor, repeatability is in 90% left and right.
In addition, adopt the preparation method of matte nesa coating of the present invention to be applied in silicon-based film solar cells production, the short circuit current that can learn solar cell from table 2 can improve 5%～10%, and then the electricity conversion of solar cell is also improved.
Obviously, those skilled in the art can carry out various changes and modification and not depart from the spirit and scope of the present invention the present invention.Like this, if within of the present invention these are revised and modification belongs to the scope of the claims in the present invention and equivalent technologies thereof, the present invention is also intended to comprise these changes and modification interior.
Claims (11)
1. a preparation method for matte nesa coating, is characterized in that, comprising:
The substrate temperature that is formed with nesa coating is adjusted to 18 ℃～25 ℃;
In acid solution, the nesa coating of adjusting after temperature is carried out to making herbs into wool, making herbs into wool duration is 30～100 seconds, wherein, described acid solution by weight percentage, contain 0.0365%～0.365% hydrogen chloride, 0.04%～0.4% hydrogen fluoride, 0.1%～0.5% oxalic acid and 0.1%～0.5% acetic acid;
Nesa coating after making herbs into wool is cleaned.
2. the preparation method of matte nesa coating as claimed in claim 1, is characterized in that, described acid solution contains 0.0365%～0.182% hydrogen chloride, 0.04%～0.2% hydrogen fluoride, 0.1%～0.3% oxalic acid and 0.1%～0.3% acetic acid.
3. the preparation method of matte nesa coating as claimed in claim 2, is characterized in that, described acid solution contains 0.182% hydrogen chloride, 0.08% hydrogen fluoride, 0.2% oxalic acid and 0.1% acetic acid; Or described acid solution contains 0.0365% hydrogen chloride, 0.04% hydrogen fluoride, 0.1% oxalic acid and 0.1% acetic acid; Or described acid solution contains 0.182% hydrogen chloride, 0.2% hydrogen fluoride, 0.3% oxalic acid and 0.3% acetic acid.
4. the preparation method of matte nesa coating as claimed in claim 1, is characterized in that, described making herbs into wool duration is 30 seconds, 50 seconds, 60 seconds, 100 seconds or 120 seconds.
5. the preparation method of matte nesa coating as claimed in claim 1, it is characterized in that, describedly the substrate temperature that is formed with nesa coating is adjusted to 18 ℃～25 ℃ is specially: the substrate that is formed with nesa coating is infiltrated in the deionized water of 18 ℃～25 ℃, make its temperature be adjusted to 18 ℃～25 ℃.
6. the preparation method of matte nesa coating as claimed in claim 1, it is characterized in that, describedly the substrate temperature that is formed with nesa coating is adjusted to 18 ℃～25 ℃ is specially: the substrate temperature that is formed with nesa coating is adjusted to 18 ℃, 20 ℃ or 25 ℃.
7. the preparation method of matte nesa coating as claimed in claim 1, is characterized in that, described nesa coating adopts the method for magnetron sputtering plating to form on substrate.
8. the preparation method of the matte nesa coating as described in claim 1～7 any one, is characterized in that, the material of described nesa coating is Al-Doped ZnO, and wherein the doping content of aluminium is 1%～1.2%.
9. the preparation method of matte nesa coating as claimed in claim 8, is characterized in that, the thickness of described nesa coating is 700～1200nm.
10. the preparation method of matte nesa coating as claimed in claim 9, is characterized in that, the thickness of described nesa coating is 700nm, 900nm, 1000nm or 1200nm.
11. 1 kinds of matte nesa coatings, is characterized in that, the preparation method by the matte nesa coating as described in claim 1～10 any one obtains.
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